Viscoelastic Behaviour

of Polymers
 Objectives

 Discuss common forms of viscoelastic behaviour

 Discuss phenomena in terms of deformation of elastic solids with

focus on linear viscoelasticity

 Discuss phenomenological mechanical models of viscoelasticity

 Experimental determination of parameters

Introduction
 Polymers

 Word Polymer originates from Greek word

polymeros, meaning many membered

 Often word Polymer is thought of composed of

two words

 Poly meaning many

 mer meaning unit

 Thus Polymer means many units describing a

polymer molecule
 Polymers Classification

 Thermoplastics (linear)
 Have only secondary bonds between chains

 Can be melted and molded

 Examples: Polyvinyl Chloride(PVC), Polystyrene

(PS)

 Thermosets (crosslinked)
 Have primary and secondary bonds between
chains

 Not possible to melt and mold

 Examples: Epoxides, Polyesters

 Polymers Definitions

 Structure
 Amorphous: when polymer chains are arranged randomly in no particular order
 Crystalline: when polymer chains are arranged in an orderly manner
 Glass transition temperature
 Not same as melting. Melting happens in crystalline polymers
 It’s a transition that happens in amorphous polymers
 A reversible transition from a hard and relatively brittle state into a soften or
rubber like state
 Cross-linking
 A bond that links one polymer chain to other. Once cross linking takes place, the
material can no longer be shaped.
 Curing
 Toughening or hardening of a polymer material by cross-linking of polymer chains
 Stiffness of Polymers

 Much engineering design – particularly with polymers – is based on

stiffness

 Designer aims to keep the elastic deflections below some critical limit

 Material property which is most important is Young’s modulus, E

 Metals and ceramics have Young’s moduli which, near room

temperature, can be thought of as constant

 This is not true for polymers. Polymers have time and temperature
dependent modulus

 The modulus E of a polymer can change by as much as a factor of

1000 when the temperature is changed
 Glassy regime, with a large
modulus, around 3 GPa

Glass-transition regime,
in which the modulus
drops steeply from 3
GPa to around 3 MPa

Rubbery Viscous regime, when the

regime, with a polymer starts to flow
low modulus,
around 3 MPa

Regime of
decomposition in
which chemical
Five regimes of deformation in linear-amorphous polymers breakdown starts
 Viscoelasticity

 Two main types of ideal materials

 Elastic solid

 Has a definite shape and deforms under external forces

 Stores all energy that is obtained from external forces

 Stored energy restores the original shape once the force is removed

 Viscous liquid

 No definite shape

 Flows irreversibly under the action of external forces

 Viscoelasticity

 A polymer can exhibit all intermediate range of properties between

an elastic solid and a viscous liquid

 Properties depends on temperature and experimental time scale

 Material response which combines both liquid and solid like features
is termed Viscoelasticity

 Implies that the mechanical properties are a function of time due to

intrinsic nature of the material and

 Material possess a memory (fading) of past events

Linear
Viscoelastic
Behaviour
 Linear Viscoelastic Behaviour

 Newton’s law of viscosity defines viscosity 𝜂 as

𝜕𝑉
𝜎=𝜂 Velocity gradient in liquid
𝜕𝑦

𝑉 is velocity, 𝑦 is direction of velocity gradient

 For velocity gradient in xy plane

𝜕𝑉𝑥 𝜕𝑉𝑦
𝜎𝑥𝑦 = 𝜂 +
𝜕𝑦 𝜕𝑥

 Since
𝜕𝑢 𝜕𝑣
𝑉𝑥 = 𝑎𝑛𝑑 𝑉𝑦 = 𝑤ℎ𝑒𝑟𝑒 𝑢 𝑎𝑛𝑑 𝑣 𝑎𝑟𝑒 𝑑𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡𝑠 𝑖𝑛 𝑥 𝑎𝑛𝑑 𝑦 𝑑𝑖𝑟𝑒𝑐𝑡𝑖𝑜𝑛
𝜕𝑡 𝜕𝑡
 Linear Viscoelastic Behaviour

 Thus
𝜕 𝜕𝑢 𝜕 𝜕𝑣
𝜎𝑥𝑦 =𝜂 +
𝜕𝑦 𝜕𝑡 𝜕𝑥 𝜕𝑡
𝜕 𝜕𝑢 𝜕𝑣
𝜎𝑥𝑦 = 𝜂 +
𝜕𝑡 𝜕𝑦 𝜕𝑥
𝜕𝑒𝑥𝑦
𝜎𝑥𝑦 =𝜂
𝜕𝑡

 Thus shear stress is directly proportional to rate of change of shear

strain with time
 In Hook’s law, stress is linearly related to stain
 In Newton’s law for viscosity, stress is linearly related to rate of change
of strain or strain rate
 Linear Viscoelastic Behaviour

 A simple constitutive relation for behaviour of a linear viscoelastic

solid is obtained by combining the two laws

𝜕𝑒𝑥𝑦
𝜎𝑥𝑦 = 𝐺𝑒𝑥𝑦 + 𝜂
𝜕𝑡

 The equation represents the Kelvin or Voigt model for linear viscoelastic
solid

 Hook’s law is valid only for small strains

 Newton’s law of viscosity is valid for small flow rates
 Most useful plastics show some non-linearity at strains around 1 percent
 Linear Viscoelastic Behaviour

 Two main phenomena observed in materials as a result of

viscoelastic deformation are

 Creep

 Stress Relaxation
 Creep

 Tendency of a solid material to move slowly or deform under the

influence of mechanical stresses

 Occurs as a result of long-term exposure to high levels of stress that

are still below the yield strength of the material

 Not to be confused with metallic creep

 Creep in polymers at low strains (1 percent) is essentially recoverable

after unloading
 Creep

 Response of a linear elastic solid under two levels of stress

 Strains follows the pattern of loading programme exactly

 Strain is in exact proportionality to the applied stress
 Creep

 Response of a linear viscoelastic solid under two levels of stress

Creep

 Total strain 𝑒 is sum of three parts

 𝑒1 immediate elastic deformation
 𝑒2 delayed elastic deformation
 𝑒3 Newtonian flow
 Creep

 Since the material shows linear behaviour, the magnitudes of 𝑒1 , 𝑒2

and 𝑒3 are exactly proportional to applied stress

 Creep compliance 𝑱 𝒕 , which is function of time, is defined as

𝑒(𝑡)
𝐽 𝑡 = = 𝐽1 + 𝐽2 + 𝐽3
𝜎

 Linear amorphous polymers

 Significant 𝐽3 creep above 𝑇𝑔 where creep may continue till material
fracture
 At lower temperatures, 𝐽1 and 𝐽2 dominates
 Cross linked and crystalline polymers do not show 𝐽3 term
 Log Creep Compliance vs
Log Time
At very short times,
compliance is that
of a glassy solid and
is independent of
time
At intermediate
times, compliance
is time dependent
and behaviour is
viscoelastic
At very long times,
compliance is that
of a rubber like solid
and is independent
of time

Retardation time 𝜏 can be

defined in middle of viscoelastic 𝜏 is very small at room temperature for rubbery materials
region to characterise the time-
𝜏 is very large at room temperature for glassy materials
scale for creep
 Creep and Recovery

 At any selected time, the extent of recovery is directly proportional

to the formerly applied stress

 Recovery behaviour is basically similar to the creep behavior if we

neglect the quantity 𝑒3 (Newtonian flow)

 Direct consequence of linear viscoelastic behaviour

Recovery
 Stress Relaxation

 When instantaneous strain is applied to an ideal elastic solid, finite

and constant stress will be recorded
 For a linear viscoelastic solid, the instantaneous stress will be
proportional to applied strain and will decrease with time
 Stress Relaxation

 Stress Relaxation Modulus may be define as

𝜎(𝑡)
𝐺 𝑡 =
𝑒

 For amorphous linear polymers at high temperatures, the stress may

eventually decay to zero

 If there is no viscous flow, the stress decays to a finite value

 Gives an equilibrium or relaxed modulus 𝐺𝑟 at finite time

 Log Relaxation Modulus vs
Log Time

At very long times,

Relaxation Modulus
At intermediate is that of a rubber
times, Relaxation like solid and is
Modulus is time independent of
dependent and time
behaviour is
At very short viscoelastic
times, Relaxation
Modulus is that of
a glassy solid and
is independent of
time
The relaxation time 𝜏 and retardation time 𝜏 are
Relaxation time 𝜏 can of the same general magnitude, but identical
be defined in middle of only for simpler models
viscoelastic region
Mathematical
Modelling of
Linear
Viscoelasticity
 Mathematical Modelling

 Phenomenological models: have no direct relationship with

chemical composition or molecular structure

 Enable response to a complicated loading pattern to be

deduced from a single creep or stress-relaxation plot

 Models validity depend upon the assumptions of linear

viscoelasticity

 Assumption: Total deformation can be considered as sum of

independent elastic and viscous components
 Mathematical Modelling

Boltzmann Superposition Principle

 Creep is a function of entire past loading history
 Each loading step makes an independent contribution to final
deformation
 Total deformation is the sum of all deformation contributions

Creep behaviour
of a viscoelastic
solid under multi-
step loading

𝑇1 𝑇2 𝑇3 𝑡
 Mathematical Modelling

 Total creep at time 𝑡

𝑒 𝑡 = Δ𝜎1 𝐽(𝑡 − 𝑇1 )+Δ𝜎2 𝐽(𝑡 − 𝑇2 )+Δ𝜎3 𝐽(𝑡 − 𝑇3 )+…

Creep
compliance

𝑡
𝑒 𝑡 = 𝐽(𝑡 − 𝑇) 𝑑𝜎(𝑇)
−∞ 𝑇1 𝑇2 𝑇3 𝑡

 Above can be written by separating instantaneous elastic response

in terms of the unrelaxed modulus 𝐺𝑢
𝑡
𝜎 𝑑𝜎(𝑇)
𝑒 𝑡 = + 𝐽(𝑡 − T) 𝑑𝑇
𝐺𝑢 −∞ 𝑑𝑇
 Concept Check Point

 Consider a strain loading programme with strain increments of Δ𝑒1 ,

Δ𝑒2 , Δ𝑒3 added at times 𝑇1 , 𝑇2 , 𝑇3 respectively
 Using the Boltzmann Superposition principle, write expression for total
stress at time 𝑡
 Hint: use the analogy with the total strain equation

𝑒 𝑡 = Δ𝜎1 𝐽(𝑡 − 𝑇1 )+Δ𝜎2 𝐽(𝑡 − 𝑇2 )+Δ𝜎3 𝐽(𝑡 − 𝑇3 )+…

Answer

𝜎 𝑡 = Δ𝑒1 𝐺(𝑡 − 𝑇1 )+Δ𝑒2 𝐺(𝑡 − 𝑇2 )+Δ𝑒3 𝐺(𝑡 − 𝑇3 )

 General Equation of Linear
Viscoelasticity

 The Boltzmann superposition principle is one starting point for a

theory of linear viscoelastic behavior
 It is sometimes called the ‘integral representation of linear
viscoelasticity’ because it defines an integral equation
 An equally valid starting point is to relate the stress to the strain by a
linear differential equation
 This leads to a differential representation of linear viscoelasticity
 In its most general form, the equation is expressed as

where P and Q are linear differential operators with respect to time

 General Equation of Linear
Viscoelasticity

 Most generally the differential equation is

𝑑𝜎 𝑑2 𝜎 𝑑𝑒 𝑑2 𝑒
𝑎0 𝜎 + 𝑎1 + 𝑎2 2 + ⋯ = 𝑏0 𝑒 + 𝑏1 + 𝑏2 2 + ⋯
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡

 Often adequate to represent the experimental data by including

only one or two terms on each side of this equation

 This is equivalent to describing the viscoelastic behaviour by

mechanical models constructed of mechanical components
Mechanical
Models
 Mechanical Models

 Viscoelastic behaviour can be described by mechanical models

constructed using elastic springs and viscous dashpots

 Elastic springs follow Hooke’s law

𝜎 = 𝐸𝑒

 Viscous dashpots follow Newton’s law of viscosity

𝜕𝑒𝑥𝑦
𝜎𝑥𝑦 = 𝜂
𝜕𝑡
 Kelvin or Voigt Model

 Consists a spring of modulus 𝐸𝑘 and a dashpot

of viscosity 𝜂𝑘 𝜎

 Constant stress 𝜎 is applied at 𝑡 = 0

𝐸𝑘 𝜂𝑘
 Stress is shared by both components 𝜎1 , 𝑒1 𝜎2 , 𝑒2
 Due to dashpot, instantaneous extension can
not happen

 Deformation occurs at a varying rate

 After a time, depending on viscosity, spring

reaches maximum extension
 Kelvin or Voigt Model

 Recovery occurs as stress is removed

Recovery
 No instantaneous retraction

 Thus stress for spring and dashpot

𝑑𝑒2
𝜎1 = 𝐸𝐾 𝑒1 𝜎2 = 𝜂𝐾
𝑑𝑡

 Total stress 𝜎 = 𝜎1 + 𝜎2

 Total strain 𝑒 = 𝑒1 = 𝑒2

 Thus 𝑑𝑒
𝜎 = 𝐸𝐾 𝑒 + 𝜂𝐾
𝑑𝑡
 Kelvin or Voigt Model

 Solving for 0 < t < t1, when the stress is σ

𝜂𝐾
 where has the dimensions of time, and represents the rate at
𝐸𝐾
which the deformation occurs: it is the retardation time 𝜏
 By Integration
 Kelvin or Voigt Model

 An expression for strain can be obtained in the form

𝜎 𝑡
𝑒= [1 − exp − ]
𝐸𝐾 𝜏

where 𝜏 is the retardation time

𝑡
 In terms of compliance 𝑒 = 𝐽𝜎[1 − exp − ]
𝜏

 For t > t1 after unloading, the solution becomes

 Kelvin or Voigt Model

 The retardation time 𝜏 is the time after loading for the strain to reach

of its equilibrium value; after stress removal the strain decays to

(1/exp(0)) of its maximum value in time 𝜏

Limitations
 Kelvin model is unable to describe stress relaxation: At constant strain
dashpot can not relax
𝑑𝑒 𝑑𝑒
= 0 𝑡ℎ𝑢𝑠 𝜎 = 𝐸𝐾 𝑒 + 𝜂𝐾 = 𝐸𝐾 𝑒
𝑑𝑡 𝑑𝑡
 Maxwell Model

 Consists of a spring and dashpot in series 𝜎

 Total stress 𝜎 = 𝜎1 = 𝜎2
𝐸𝑚 , 𝜎1 , 𝑒1
 Total strain 𝑒 = 𝑒1 + 𝑒2
𝑑𝜎 𝑑𝑒1 𝜂𝑚 , 𝜎2 , 𝑒2
 Stress can be written as 𝜎1 = 𝐸𝑚 𝑒1 ⇒ = 𝐸𝑚
𝑑𝑡 𝑑𝑡
𝑑𝑒 1 𝑑𝜎 𝜎
 Thus, total strain rate = + Creep & recovery
𝑑𝑡 𝐸𝑚 𝑑𝑡 𝜂𝑚 behaviour

Strain
 Considering stress relaxation

𝑑𝑒 1 𝑑𝜎 𝜎 𝑑𝜎 𝐸𝑚
= 0 𝑠𝑜 0 = + 𝑡ℎ𝑢𝑠 =− 𝑑𝑡
𝑑𝑡 𝐸𝑚 𝑑𝑡 𝜂𝑚 𝜎 𝜂𝑚
Time
 Maxwell Model

 At time t=0, 𝜎 = 𝜎0 (initial stress). After integrating 𝜎

𝐸𝑚 , 𝜎1 , 𝑒1

𝜂𝑚 , 𝜎2 , 𝑒2
 This equation shows that the stress decays
𝜂
exponentially with a characteristic time constant m
𝐸m

𝑡
𝜎 = 𝜎0 exp −
𝜏

where 𝜏 is the relaxation time

 Maxwell Model

𝜎
Limitations
𝐸𝑚 , 𝜎1 , 𝑒1
 Under constant stress (creep)
𝜂𝑚 , 𝜎2 , 𝑒2
𝑑𝜎 𝑑𝑒 𝜎
= 0 𝑡ℎ𝑢𝑠 =
𝑑𝑡 𝑑𝑡 𝜂𝑚

where Newtonian flow is observed which is generally not true for

viscoelastic materials

 Stress relaxation behaviour cannot be usually represented by a

single exponential decay term
Maxwell Model
 The Standard Linear Solid

 Consider the general linear differential equation

𝑑𝜎 𝑑2 𝜎 𝑑𝑒 𝑑2 𝑒
𝑎0 𝜎 + 𝑎1 + 𝑎2 2 + ⋯ = 𝑏0 𝑒 + 𝑏1 + 𝑏2 2 + ⋯
𝑑𝑡 𝑑𝑡 𝑑𝑡 𝑑𝑡

 To obtain even an approximate description of both stress relaxation

and creep, at least the first two terms on each side of Equation must
be retained
 The simplest equation will be of the form

𝑑𝜎 𝑑𝑒
𝑎0 𝜎 + 𝑎1 = 𝑏0 𝑒 + 𝑏1
𝑑𝑡 𝑑𝑡
 The Standard Linear Solid

𝑑𝜎 𝑑𝑒
𝑎0 𝜎 + 𝑎1 = 𝑏0 𝑒 + 𝑏1
𝑑𝑡 𝑑𝑡

 This will be adequate to a first approximation for creep (when dσ/dt

= 0) and

 for stress relaxation (when de/dt = 0), giving an exponential response

in both cases
 The Standard Linear Solid

 Kelvin and Maxwell models can not define the general behaviour of
viscoelastic solid completely
 A more real model is obtained by adding a second spring in parallel
with a Maxwell unit
 In creep, both spring extend
1 1 𝐸𝑚
𝜏 = 𝜂𝑚 + 𝐸𝑎
𝐸𝑎 𝐸𝑚
𝜂𝑚
 In stress relaxation, 𝐸𝑎 is unaffected
𝜂𝑚
𝜏=
𝐸𝑚
𝑑𝜎 𝑑𝑒
 Stress strain relationship is given by 𝜎+𝜏 = 𝐸𝑎 𝑒 + (𝐸𝑎 + 𝐸𝑚 )𝜏
𝑑𝑡 𝑑𝑡
 The Standard Linear Solid

Limitations

 Standard linear solid model predicts an exponential response only

 To describe the observed viscoelastic behaviour quantitatively

would require the inclusion of many terms in the linear differential
equation

 These more complicated equations are equivalent to either a large

number of Maxwell elements in parallel or a large number of Voigt
elements in series
 Concept Check Point

 How would this model predict the creep and relaxation response?
Dynamical THE COMPLEX MODULUS
Mechanical AND

Measurements COMPLEX COMPLIANCE

 Complex Modulus and
Complex Compliance

 To characterise the viscoelastic behaviour, material is sinusoidally

deformed and resulting stress is recorded
 For linear viscoelastic behaviour, stress and strain will vary sinusoidally
 For an ideal elastic material, stress and strain are in phase i.e. phase
shift 𝛿 = 0
 For an ideal viscous material, stress and strain are 90° out of phase
𝛿 = 90
 Strain lags behind stress

𝑆𝑡𝑟𝑎𝑖𝑛 𝑒 = 𝑒0 sin 𝜔𝑡
𝑆𝑡𝑟𝑒𝑠𝑠 𝜎 = 𝜎0 sin(𝜔𝑡 + 𝛿)

where 𝜔 is frequency and 𝛿 is phase lag

 Complex Modulus and
Complex Compliance

 So stress can be written as

𝜎 = 𝜎0 cos 𝛿 sin 𝜔𝑡 + 𝜎0 sin 𝛿 cos 𝜔𝑡

 For viscoelastic material, stress has two components

 First of magnitude 𝜎0 cos 𝛿 in phase with strain
 Second of magnitude 𝜎0 sin 𝛿 which is 90° out of phase with strain

 Stress-strain relation can be defined by

𝐺∗
 𝐺1 in phase with strain 𝐺2
 𝐺2 90° out of phase with strain
𝛿
𝜎0 𝜎0
𝐺1 = cos 𝛿 𝐺2 = sin 𝛿 𝐺1
𝑒0 𝑒0
Phasor diagram
 Complex Modulus and
Complex Compliance

 A phasor diagram indicate that 𝐺1 and 𝐺2 define a complex

modulus 𝐺 ∗

 If 𝑒 = 𝑒0 exp 𝑖𝜔𝑡 𝑎𝑛𝑑 𝜎 = 𝜎0 exp[𝑖 𝜔𝑡 + 𝛿 ]

 Thus 𝜎 𝜎0 𝜎0
∗
𝐺 = = exp 𝑖𝛿 = (cos 𝛿 + 𝑖 sin 𝛿) = 𝐺1 + 𝑖𝐺2
𝑒 𝑒0 𝑒0

 𝐺1 , in phase with strain, is called storage modulus

 Defines the energy stored in specimen due to applied strain

 𝐺2 , which is 𝜋 2 out of phase with strain, is called loss modulus

 Defines the dissipation of energy
 Complex Modulus and
Complex Compliance

 Calculating the energy dissipated per cycle, ∆𝑬

2𝜋/𝜔
𝑑𝑒
∆𝐸 = 𝜎 𝑑𝑒 = 𝜎 𝑑𝑡
0 𝑑𝑡
2𝜋/𝜔
 Subtituting for 𝜎 and 𝑒 ∆𝐸 = 𝜔𝑒02 𝐺1 sin 𝜔𝑡 cos 𝜔𝑡 + 𝐺2 cos 2 𝜔𝑡 𝑑𝑡
0
 Solving the integral we get ∆𝐸 = π𝐺2 𝑒02

 If integral for ∆𝐸 is evaluated over a quarter cycle rather than over

the complete period, the first term
2𝜋/𝜔
𝜔𝑒02 𝐺1 sin 𝜔𝑡 cos 𝜔𝑡 𝑑𝑡
0
1
gives the maximum stored elastic energy, E 𝐸 = 𝐺1 𝑒02
2
 Complex Modulus and
Complex Compliance

 The ratio of loss modulus to storage modulus can be written as

𝐺2 ∆𝐸 Where ∆𝐸 is energy dissipated per cycle
= tan 𝛿 =
𝐺1 2𝜋𝐸 and E is maximum stored elastic energy

∆𝐸 ∆𝐸
 The ratio is called specific loss = 2𝜋 tan 𝛿
𝐸
𝐸
 Typical values of 𝐺1 , 𝐺2 and tan 𝛿 for a polymer are 109 Pa, 107 Pa
and 0.01
 In such cases, 𝐺 ∗ is approximately equal to 𝐺1
 Similarly, complex compliance can be developed

𝐽∗ = 𝐽1 + 𝑖𝐽2 Where 𝐺 ∗ = 1 𝐽∗
 Response of a Sample to
Sinusoidal Shear Strain

𝜎0 𝜎0
 𝐺1 is stress measured at 𝐺1 = cos 𝛿 𝐺2 = sin 𝛿
maximum strain divided by 𝑒0 𝑒0
applied strain amplitude 𝛾𝑜

 𝐺2 is stress measured at zero

strain divided by applied strain
amplitude 𝛾𝑜

 Strain is zero but stress in

general won’t be zero

 Rate of strain is maximum

when strain passes through
zero
 Response of a Sample to
Sinusoidal Shear Strain

 Stress at zero strain is result of

sample responding to strain
rate as would a purely viscous
material (free flow, no strain
produced)

 As strain reaches its peak,

strain rate approaches to
zero

 Sample at this point must only

be responding to strain as
would an elastic material
 Creep Compliance & Stress
Relaxation Modulus

 As a consequence of Boltzmann superposition principle, a

relationship between creep compliance and stress relaxation
modulus exits
 In time independent functions, compliance and modulus are simply
reciprocal to each other
 This no longer holds in time dependent case
 The general solution is given by

𝑡
𝑡= 𝐺 𝑠 𝐽 𝑡 − 𝑠 𝑑𝑠
0

Calculated using Laplace transformation

 Creep Compliance & Stress
Relaxation Modulus

 Relationship between
creep compliance and
stress relaxation modulus

 Shapes of the two curves

are markedly different

 The two would be mirror

images if reciprocally
related
Example
Problems
 Problem 1

 Stress relaxation modulus of a certain polymer can be described by

𝐺 𝑡 = 𝐺0 𝑒 −𝑡/𝜏

And has the values 2.0 GPa and 1.0 GPa at t=0 and 104 sec
respectively. Calculate the form of the creep compliance and so
evaluate the strain 1000 sec after the rapid application of a stress of 100
MPa.
𝜎
SOLUTION

 The stress relaxation term is the form of Maxwell element 𝐸

and
𝜂 𝜂
𝐺 𝑡 = 𝐸𝑒 −𝑡/𝜏 𝜏= 𝐸
 Problem 1

 At t=0 𝐺 𝑡 = 𝐸𝑒 −𝑡/𝜏 = 𝐸 = 2.0 𝐺𝑃𝑎 (given)

 At t=104 𝐺 𝑡 = 𝐸𝑒 −𝑡/𝜏 = 2𝑒 −10

4 /𝜏
= 1.0 𝐺𝑃𝑎 (given)

104 /𝜏
104
𝑒 =2⇒ = 𝑙𝑛𝑒 2 = 0.693
𝜏
104 𝜂 2 × 104
𝜏= = ⇒𝜂= 𝐺𝑃𝑎 𝑠
0.693 𝐸 0.693 𝜎

 Total strain 𝜀 = 𝜀𝐸 + 𝜀𝑣
𝐸
𝜎𝑡
 For viscous element 𝜀𝑣 =
𝜂
𝜂
 Total strain 𝜎 𝜎𝑡 1 𝑡
𝜀 𝑡 = + =𝜎 +
𝐸 𝜂 𝐸 𝜂
 Problem 1

 Putting 𝐽0 = 1/𝐸
𝑡
𝐽 𝑡 = 𝐽0 +
𝜂

1 103 × 0.693
𝜀 1000 = 0.1 + = 0.1(0.5 + 0.0347)
2 2 × 104

𝜀 1000 = 5.35 𝑝𝑒𝑟𝑐𝑒𝑛𝑡 𝜎

𝜂
 Problem 2

 The creep deformation of a linear viscoelastic solid under constant

stress can be represented by the model shown, in which spring is in
series with a Kelvin unit
𝑀1
𝑀2
𝜎

𝜂
Here, 𝑀1 and 𝑀2 represent Young’s moduli, 𝜂 the viscosity and 𝜎 the
total constant stress. Show that the total strain is dependent on the
relaxation time, 𝜏1 = 𝜂 𝑀1and is given by

𝜎 𝜎 𝑡
𝜀= + [1 − exp − ]
𝑀2 𝑀1 𝜏1
 Problem 2

Immediately after applying stress, the strain is 0.002; after 1000 sec the
strain is 0.004; after a very long time the strain tends to 0.006. What is the
retardation time 𝜏1 ?

Note: It is not necessary to know the stress or the values of 𝑀1 , 𝑀2 and 𝜂

SOLUTION

 When load is applied, spring 2 extends by 𝜎 𝑀2 and remains stretched

 Time dependency is due entirely to the Kelvin unit, where

 In Kelvin unit, total strain 𝑒 = 𝑒𝐸 = 𝑒𝑉

 In Kelvin unit, Total stress 𝜎 = 𝜎𝐸 + 𝜎𝑉
 Problem 2

 Thus 𝑑𝜀
𝜎𝐸 = 𝑀1 𝜀 𝜎𝑉 = 𝜂
𝑑𝑡
𝑑𝜀 𝜎 𝜂 𝑑𝜀
𝜎 = 𝑀1 𝜀 + 𝜂 ⇒ =𝜀+
𝑑𝑡 𝑀1 𝑀1 𝑑𝑡

 Rearranging
𝜀 𝑡 𝜀
𝑑𝜀 𝑀1 𝜎 𝑀1 𝜀 𝑀1
𝜎 = 𝑑𝑡 ⇒ −𝑙𝑛 −𝜀 = 𝑡 ⟹ ln 1 − =− 𝑡
0 ( − 𝜀) 𝜂 0
𝑀1 0
𝜂 𝜎 𝑀1 𝜂
𝑀1

 where 𝜂 𝑀1 is the relaxation time 𝜏1

𝜀 𝜎
1− = exp − 𝑡 𝜏1 ⟹ 𝜀 = [1 − exp − 𝑡 𝜏1 ]
𝜎 𝑀1 𝑀1
 Problem 2

 Total strain is obtained by adding instantaneous deformation of

Spring 2
𝜎 𝜎
𝜀= + [1 − exp − 𝑡 𝜏1 ]
𝑀2 𝑀1
𝜎
 At time t=0 𝜀= = 0.002 (𝑔𝑖𝑣𝑒𝑛)
𝑀2
𝜎 𝜎
 As t tends to infinity 0.006 = 0.002 + ⇒ = 0.004
𝑀1 𝑀1

 At time t=1000 sec 0.004 = 0.002 + 0.004[1 − exp − 𝑡 𝜏1 ]

1 − exp − 𝑡 𝜏1 = 0.5 ⇒ exp − 𝑡 𝜏1 = 0.5 ⟹ exp 𝑡 𝜏1 = 2

1000
𝑡 𝜏1 = 𝑙𝑛𝑒 2 = 0.693 ⟹ 𝜏1 = = 1440 𝑠𝑒𝑐
0.693
 Problem 3

 A strip of linear viscoelastic polymer 200 mm long, 10 mm wide and 1 mm

thick and with an extensional Young’s modulus of 2 GPa, is mounted in a
dynamic testing apparatus. The specimen is initially extended by 1 mm,
and then subjected to a sinusoidally varying strain with an amplitude of
± 1 mm.

 At 20°C and 5 Hz the phase lag between stress and strain is 0.1 rad.
Calculate the maximum stress developed, the elastic energy stored
during the positive quarter cycle and the work dissipated per cycle

 Another specimen of the same polymer is tested in a simple torsion

pendulum at 20°C. The period of vibration is 2 sec and the logarithmic
decrement is 0.2. What would you expect the phase lag in a dynamic
tester to be at 20°C and 0.5 Hz?
 Problem 3

SOLUTION

 The maximum stress occurs at 1 percent extension

𝜎 = 2 × 109 × 0.01 = 20 𝑀𝑃𝑎

 Thus amplitude of vibrating stress 𝜎0 = ±10 𝑀𝑃𝑎

 and amplitude of vibrating strain 1

𝜀0 = = 0.005
200

1
 Maximum stored elastic energy 𝐸= 𝐴𝐿𝜎0 𝜀0 cos 𝛿 = 0.005
2

𝐴𝑒𝑟𝑎 = 𝐴 = 10−5 𝑚2 𝐿𝑒𝑛𝑔𝑡ℎ = 𝐿 = 0.2 𝑚

 Problem 3

 Phase lag tan 𝛿 = 0.1 ≈ sin 𝛿

cos 𝛿 = (1 − 0.01)1 2 ≈ 0.995

1
𝐸= × 10−5 × 0.2 × 107 × 5 × 10−3 × 0.995 ≈ 5 × 10−2 𝐽
2

 Energy dissipated per cycle

∆𝐸 = 𝜋𝐴𝐿𝜎0 𝜀0 sin 𝛿

∆𝐸 = 𝜋 × 10−5 × 0.2 × 107 × 5 × 10−1 ≈ 3.1 × 10−2 𝐽

 At 0.5 Hz, logarithmic decrement = 0.2

0.2
0.2 = 𝜋 tan 𝛿0.5 ⟹ tan 𝛿0.5 = = 0.064 (Phase lag)
𝜋
Measurement
of
Viscoelasticity
 Measurement of Viscoelastic Behaviour

 Five main classes of experiments

 Transient measurements: creep and stress relaxation

 Low frequency vibrations: free oscillations methods

 High frequency vibrations: resonance methods

 Forced vibration non-resonance methods

 Wave propagation methods

 Measurement of Viscoelasticity

 Creep Experiment
 Sample is subjected to constant shear stress and
its shear strain is measured as a function of time
 Shear compliance is given by

𝛾(𝑡)
𝐽 𝑡 =
𝜎0

 Thermal equilibrium should be attained before

starting the experiment
 Commercial instruments use low inertia, low
friction, constant torque motor instead of
weights
Creep Measurement
 Measurement of Viscoelasticity

 Stress Relaxation Test

 Strain is kept constant and stress is measured as
a function of time
 Relaxation modulus is given by

𝜎(𝑡)
𝐸 𝑡 =
𝜀0
 Sample is heated to desired temperature and
thermal equilibrium is achieved
 Latch is released and spring stretches the
sample until the stop is reached
 Relationships between stiffness and
compliance are not valid 𝜎(𝑡) 𝜎0
𝐸 𝑡 = ≠
𝜀0 𝜀(𝑡)
DMA Testing Modes

Dual Cantilever Single Cantilever Compression

Sample
Clamp / Support

Shear Tension
DMA Test Equipment
 References

 An Introduction to The Mechanical Properties of Solid Polymers, 2nd

Ed, I. M. Ward, J. Sweeney, John Wiley & Sons, 2004
 (Ch 4, Ch 5, Ch 6)
 Mechanical Behaviour of Materials, 2nd Ed, Marc Meyers and
Krishan Chawla, Cambridge University Press, 2009
 (Ch 2.12)